CN117050513A - Super-tough nylon special for blow molding - Google Patents
Super-tough nylon special for blow molding Download PDFInfo
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- CN117050513A CN117050513A CN202310726803.4A CN202310726803A CN117050513A CN 117050513 A CN117050513 A CN 117050513A CN 202310726803 A CN202310726803 A CN 202310726803A CN 117050513 A CN117050513 A CN 117050513A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 57
- 229920001778 nylon Polymers 0.000 title claims abstract description 57
- 238000000071 blow moulding Methods 0.000 title description 7
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000013138 trimesic acid-based metal-organic framework Substances 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000009461 vacuum packaging Methods 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000012621 metal-organic framework Substances 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010128 melt processing Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 229920002292 Nylon 6 Polymers 0.000 description 24
- 239000000047 product Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- -1 PA9 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to a special super-tough nylon capable of being blow molded, which is based on common nylon PA6 and comprises the following components: 70-90 parts of PA6 resin, 10-29 parts of compatilizer, 0.5-1 part of Zn-BTC-MOF material loaded with SiO2 and other auxiliary agents. Instead of imported products, the Zn-BTC-MOF composite material loaded with SiO2 is used in the formula, and the porous characteristic of the MOF material and the loaded SiO2 can form hydrogen bonds with nylon, so that the dispersion effect of nano particles is improved, and the toughness and structural stability of the nylon are improved; the Zn-BTC-MOF material contains rich carboxyl groups, so that the compatibility of nylon and the molecular re-coupling capability of broken chains in processing are improved, and the melt processing capability of nylon is improved; the MOF-loaded silicon dioxide is prepared by adopting a TEOS precursor, and the porous structure of the MOF is fully utilized to ensure that SiO2 has higher dispersibility; can be applied to the fields of automobiles, production line production equipment and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to super-tough nylon special for blow molding.
Background
Nylon (PA), known as polyamide, has a wide variety of properties such as PA6, PA66, PA9, PA1010, etc. Nylon is the most widely used engineering plastic by virtue of its high strength, good wear resistance, good processing fluidity and other characteristics. Nylon 6 is a common engineering plastic with good performance, and can be widely applied to the fields of automobiles, machinery, buildings, electronic appliances, weaponry and the like. In the plastic industry, nylon is divided into injection molding nylon and blow molding nylon, the injection molding is a semi-finished product process of making a certain shape by pressurizing, injecting, cooling, separating and the like, the blow molding is to obtain a tubular plastic parison by extruding or injection molding plastic materials, the tubular plastic parison is placed in a split mold while hot, compressed air is immediately introduced into the parison after mold closing, the plastic parison is inflated and clinged to the inner wall of a mold, and various hollow products are obtained after cooling and demolding, so that the mechanical property requirements of the two materials on nylon materials are different from those of the injection molding, and the blow molding requires the nylon materials to have smaller tensile strength, bending strength and better toughness.
In the prior art, chinese patent CN102702733B discloses a special reinforced composite material for blow molding of a nylon air inlet pipe and a preparation method thereof, wherein ABS, HEPE, PBT, PET and other rubber and polyolefin resin are added into a nylon main material to serve as a modifier, and an inorganic filler is added into the nylon main material to serve as a reinforcing agent, but polyolefin and inorganic powder are greatly different from nylon in structure, and incompatibility exists during blending, so that the performance of a blended material is affected; CN102382452a discloses a preparation method of nano modified nylon composite material, wherein the nano modifier is polyhedral oligomeric silsesquioxane (POSS), and the prepared nano material has higher toughness and strength; CN109836813B discloses nylon 6 composite material and preparation method thereof, which is modified by adipic acid grafting nano SiO 2 As one of the formulas, the nylon after processing has better compatibility, and the obtained nylon 6 composite material has excellent mechanical property and flame retardant property, but the nano-modification process can not really solve the problem of nano-particle dispersibility.
The present invention has been made in view of the above problems.
Disclosure of Invention
Aiming at the prior art, the invention provides a special super-tough nylon capable of being blow molded,
comprising the following steps: 70-90 parts of PA6 resin, 10-29 parts of compatilizer, 0.5-1 part of Zn-BTC-MOF material loaded with SiO2 and 0.5-1 part of other auxiliary agents, wherein the components are calculated according to parts by mass.
Preferably, the compatilizer is a commercially available POE grafted material;
preferably, the other auxiliary agents are antioxidants and lubricants;
preferably, the lubricant is EBS zinc stearate lubricant or silicone powder;
preferably, the PA6 is PA6 with standard viscosity of 2.5-2.7;
preferably, the support is SiO 2 Zn-BTC-MOF material of (C)The preparation method of the material comprises the following steps:
step (1) preparation of Zn-BTC-MOF by trimesic acid (H) 3 BTC) is completely dissolved in absolute ethanol, and water and Zn (NO) are added under stirring at room temperature 3 ) 2 After the solution is clarified, adding NaOH solution under stirring, stopping stirring, washing for multiple times by using a 1:1 mixed solution of secondary distilled water and absolute ethyl alcohol, drying to finally obtain Zn-BTC-MOF crystals, and further grinding into powder;
step (2) a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB) is taken and dispersed in ethanol to obtain a mixed solution, and the mixed solution is stirred uniformly by ultrasound;
step (3) adding a proper amount of Zn-BTC-MOF powder into the mixed solution in the step (2), and performing ultrasonic treatment to form a uniform suspension;
step (4) a proper amount of tetraethyl orthosilicate (TEOS) is taken and released into ethanol, then the mixture solution in the step (3) is dripped into the ethanol, the PH=9-11 of the solution is regulated by ammonia water, and the solution is stirred at room temperature; after the reaction is finished, centrifuging and washing for 2 to 5 times, and then drying in an oven at 50 to 80 ℃ to obtain a final product.
Preferably, in the step (1), trimesic acid and Zn (NO 3 ) 2 The mass ratio of the NaOH solution is 1:1.5-2:2.5-3.2;
the drying temperature in the step (1) is 50-80 ℃ and the drying time is 5-12 hours;
preferably, the mass ratio of Zn-BTC-MOF to cetyltrimethylammonium bromide is 1:0.1-0.5, wherein the mass ratio of Zn-BTC-MOF to tetraethyl orthosilicate is 1-10:1;
the invention also aims to provide a preparation method of the special super-tough nylon capable of being blow molded, which comprises the following steps:
the mass fractions of the components are calculated: 70-90% of PA6 resin, 10-29% of compatilizer, 0.5-1% of Zn-BTC-MOF material loaded with SiO2 and 0.5-1% of other auxiliary agents, mixing the components, stirring for 10min by a stirrer, putting the mixture into a preheated double-screw machine for production at the main machine rotation speed of 400r/min, and putting the produced materials into a charging basket for drying and vacuum packaging.
Technical effects
Compared with the prior art, the special super-tough nylon capable of being blown has the advantages of simple preparation process and SiO-loaded formula 2 Zn-BTC-MOF composite material of (2), utilizing porous property and loaded SiO in MOF material 2 Can form hydrogen bond with nylon, which not only increases the dispersion of nano particles, but also increases the toughness and structural stability of nylon; the Zn-BTC-MOF material contains rich carboxyl groups, so that the compatibility of nylon and the molecular re-coupling capability of broken chains in processing are improved, and the melt processing capability of nylon is improved; MOF-loaded silicon dioxide is prepared by adopting TEOS precursor, and porous structure of MOF is fully utilized to ensure SiO 2 The dispersibility is high; at the same time, is loaded with SiO 2 The Zn-BTC-MOF material has rich carboxyl and pore canal structures, and can form hydrogen bonds with nylon, so that the contact between the nylon and water molecules is reduced, and the water absorption rate of the nylon material is further reduced; meanwhile, the method provided by the invention is simple in process and can be used for mass production.
Drawings
FIG. 1 is a structural diagram of a Zn-BTC-MOF material prepared in example 1;
FIG. 2 is a SiO-supported layer prepared in example 1 2 A TEM image of a Zn-BTC-MOF material of (B);
FIG. 3 is a photograph of a SiO 2-loaded Zn-BTC-MOF material prepared in example 2;
FIG. 4 is a photograph of a nylon material blow molded plastic product prepared in example 3.
Detailed Description
The implementation of the technical solution of the present invention and the advantages thereof will be described in detail by the following specific examples, but should not be construed as limiting the scope of the implementation of the present invention.
Example 1
The special super-tough nylon capable of being blow molded comprises the following components in percentage by mass: 70% of PA6 resin, 29% of compatilizer, 0.5% of Zn-BTC-MOF material loaded with SiO2 and 0.5% of silicone powder. Wherein, the compatilizer is POE grafted material sold in the market, and is produced in advance by the middle-branch of China; PA6 is PA6 with a viscosity of 2.6, produced by constant ease in Zhejiang;
the preparation method of the SiO 2-loaded Zn-BTC-MOF material specifically comprises the following steps:
step (1) preparation of Zn-BTC-MOF 8mol of trimesic acid (H) 3 BTC) was completely dissolved in 100L of absolute ethanol, and 100L of water and 12mol of Zn (NO) were added with stirring at room temperature 3 ) 2 After the solution is clarified, adding NaOH solution with the mass fraction of 30%, wherein the mass fraction of NaOH in the NaOH solution is 24mol, stirring for 1h, stopping stirring after the reaction is completed, washing for a plurality of times by using a mixed solution with the volume ratio of distilled water to absolute ethyl alcohol of 1:1, drying in an oven for 10h, finally obtaining Zn-BTC-MOF crystals (see figure 1), and further grinding into Zn-BTC-MOF powder;
step (2) dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) in ethanol to obtain a mixed solution, and stirring uniformly by ultrasonic waves;
step (3), adding a proper amount of Zn-BTC-MOF powder into the mixed solution in the step (2), and performing ultrasonic treatment to form uniform suspension;
step (4) a proper amount of tetraethyl orthosilicate (TEOS) is taken and released into ethanol, then the mixture solution in the step (3) is dripped into the ethanol, the PH=10 of the solution is regulated by ammonia water, and the solution is stirred at room temperature; after the reaction is finished, centrifuging and washing for 3 times, and then drying in an oven at 60 ℃ to obtain a final product (see figure 2);
wherein, the mass ratio of Zn-BTC-MOF to cetyltrimethylammonium bromide is 1:0.1, and tetraethyl orthosilicate in a mass ratio of 2:1;
mixing the weighed PA6 resin, the compatilizer, the Zn-BTC-MOF material loaded with SiO2 and the silicone powder, putting the mixture into a stirrer for stirring for 10min, putting the mixture into a preheated double-screw machine for production, cooling the cut material by water at the main machine rotating speed of 400r/min, and obtaining the nylon material product.
Example 2
The special super-tough nylon capable of being blow molded comprises the following components in percentage by mass: 88% of PA6 resin, 10% of compatilizer, 1% of Zn-BTC-MOF material loaded with SiO2 and 1% of antioxidant 1010. Wherein, the compatilizer is POE grafted material sold in the market, and is produced in advance by the middle-branch of China; PA6 is PA6 with the viscosity of 2.6, and is produced by Zhejiang Hengfu, and the manufacturer of the antioxidant 1010 is Shanghai Langcu;
the preparation method of the SiO 2-loaded Zn-BTC-MOF material specifically comprises the following steps:
preparing Zn-BTC-MOF, namely completely dissolving 32mol of trimesic acid (H3 BTC) in 400L of absolute ethyl alcohol, adding 400L of water and 64mol of Zn (NO 3) 2 under stirring at room temperature, adding 30% NaOH solution with the mass fraction of 80mol of NaOH into the solution under stirring after the solution is clarified, stirring for 3 hours, stopping stirring after the reaction is finished, washing for multiple times by using a mixed solution with the volume ratio of distilled water to the absolute ethyl alcohol being 1:1, drying in an oven for 10 hours, and finally obtaining Zn-BTC-MOF crystals, and further grinding into Zn-BTC-MOF powder (see figure 3);
step (2) dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) in ethanol to obtain a mixed solution, and stirring uniformly by ultrasonic waves;
step (3), adding a proper amount of Zn-BTC-MOF powder into the mixed solution in the step (2), and performing ultrasonic treatment to form uniform suspension;
step (4) a proper amount of tetraethyl orthosilicate (TEOS) is taken and released into ethanol, then the mixture solution in the step (3) is dripped into the ethanol, the PH=9 of the solution is regulated by ammonia water, and the solution is stirred at room temperature; after the reaction is finished, centrifuging and washing for 3 times, and then drying in an oven at 80 ℃ to obtain a final product;
wherein, the mass ratio of Zn-BTC-MOF to cetyltrimethylammonium bromide is 1:0.5, and tetraethyl orthosilicate in a mass ratio of 9:1;
mixing the weighed PA6 resin, the compatilizer, the Zn-BTC-MOF material loaded with SiO2 and the antioxidant 1010, putting into a stirrer for stirring for 10min, putting into a preheated double-screw machine for production, cooling the blank by water at the main machine rotating speed of 400r/min, and obtaining the nylon material product.
Example 3
The special super-tough nylon capable of being blow molded comprises the following components in percentage by mass: 80% of PA6 resin, 18% of compatilizer, 1% of Zn-BTC-MOF material loaded with SiO2 and 1% of carbon fiber. Wherein, the compatilizer is POE grafted material sold in the market, and is produced in advance by the middle-branch of China; PA6 is PA6 with viscosity of 2.6, produced by Zhejiang Hengfei, and carbon fiber is produced by Shanghai petrochemical industry;
the preparation method of the SiO 2-loaded Zn-BTC-MOF material specifically comprises the following steps:
preparing Zn-BTC-MOF, namely completely dissolving 32mol of trimesic acid (H3 BTC) in 400L of absolute ethyl alcohol, adding 400L of water and 56mol of Zn (NO 3) 2 under stirring at room temperature, adding 30% NaOH solution with the mass fraction of 90mol of NaOH in the NaOH solution under stirring after the solution is clarified, stirring for 3 hours, stopping stirring after the reaction is finished, washing for multiple times by using a mixed solution with the volume ratio of distilled water to the absolute ethyl alcohol being 1:1, drying in an oven for 10 hours, and finally obtaining Zn-BTC-MOF crystals, and further grinding into Zn-BTC-MOF powder;
step (2) dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) in ethanol to obtain a mixed solution, and stirring uniformly by ultrasonic waves;
step (3), adding a proper amount of Zn-BTC-MOF powder into the mixed solution in the step (2), and performing ultrasonic treatment to form uniform suspension;
step (4) a proper amount of tetraethyl orthosilicate (TEOS) is taken and released into ethanol, then the mixture solution in the step (3) is dripped into the ethanol, the PH=11 of the solution is regulated by ammonia water, and the solution is stirred at room temperature; after the reaction is finished, centrifuging and washing for 3 times, and then drying in a drying oven at 50 ℃ to obtain a final product;
wherein, the mass ratio of Zn-BTC-MOF to cetyltrimethylammonium bromide is 1:0.3, and tetraethyl orthosilicate in a mass ratio of 5:1;
mixing the weighed PA6 resin, the compatilizer, the Zn-BTC-MOF material loaded with SiO2 and the carbon fiber, putting the mixture into a stirrer for stirring for 10min, putting the mixture into a preheated double-screw machine for production, cooling the cut material by water at the main machine rotating speed of 400r/min, and obtaining the nylon material product. The nylon material obtained in this example was blow molded to obtain a tubular plastic material product (see FIG. 4)
Comparative example 1
A nylon material, comprising, in mass fractions: 70.5% of PA6 resin, 29% of POE grafted material and 0.5% of silicone powder.
Mixing the weighed components, putting into a stirrer for stirring for 10min, putting into a preheated double-screw machine for production, cooling the blank by water at the main machine rotating speed of 400r/min, and obtaining the nylon material product.
Comparative example 2
A nylon material, comprising, in mass fractions: 70% of PA6 resin, 29% of POE grafted material, 0.5% of Zn-BTC-MOF material and 0.5% of silicone powder. And (3) putting the raw materials into a stirrer to stir for 10min, putting the raw materials into a preheated double-screw machine to produce, cooling the cut materials by water at the main machine rotating speed of 400r/min, and obtaining the nylon material product.
Comparative example 3
A nylon material, comprising, in mass fractions: 70% of PA6 resin, 29% of POE grafted material, 0.5% of nano SiO2 material and 0.5% of silicone powder. And (3) putting the raw materials into a stirrer to stir for 10min, putting the raw materials into a preheated double-screw machine to produce, cooling the cut materials by water at the main machine rotating speed of 400r/min, and obtaining the nylon material product.
Comparative example 4
A nylon material, comprising, in mass fractions: 70% of PA6 resin, 29% of POE grafted material, 0.1% of nano SiO2 material, 0.4% of Zn-BTC-MOF material and 0.5% of silicone powder. And (3) putting the raw materials into a stirrer to stir for 10min, putting the raw materials into a preheated double-screw machine to produce, cooling the cut materials by water at the main machine rotating speed of 400r/min, and obtaining the nylon material product.
Performance testing
The blow-moldable special super-tough nylon prepared in example 1 is tested by using GB/T standard, after being regulated for 24 hours at the temperature of 23+/-2 ℃ and the humidity of 50+/-5%, the tensile strength is tested under the condition of 50mm/min according to GB/T1040, the bending strength is tested under the condition of 10mm/min according to GB/T9341, the bending modulus is tested under the condition of 10mm/min according to GB/T9341, the notch impact strength is tested under the condition of 2.75J according to GB/T1843, the nylon material is dried after being soaked in cold water for 24 hours at the temperature of 23 ℃ and then tested, and the test results are shown in the table below.
The test results show that the special blow-moldable super-tough nylon material prepared by the invention has the advantages that the Zn-BTC-MOF composite material loaded with SiO2 endows the nylon material with lower tensile strength and bending strength, so that the product has strong plasticity, better notch impact strength and water absorption rate, and better toughness and wider applicability, and the material can be widely applied to the fields of automobile oil pipes, automatic pipeline rails and the like.
Claims (5)
1. A special super-tough nylon capable of being blow molded is characterized in that:
the components comprise: 70-90 parts of PA6 resin, 10-29 parts of compatilizer, 0.5-1 part of other auxiliary agents and the weight parts of components are calculated according to the weight parts of Zn-BTC-MOF material loaded with SiO 2;
the compatilizer is a commercially available POE grafted material;
the other auxiliary agents are an antioxidant and a lubricant;
the SiO is loaded 2 The specific preparation method of the Zn-BTC-MOF material is as follows:
step (1) preparing Zn-BTC-MOF by dissolving trimesic acid in absolute ethanol completely, adding water and Zn (NO) under stirring at room temperature 3 ) 2 After the solution is clarified, adding NaOH solution under stirring, stopping stirring, washing for multiple times by using a 1:1 mixed solution of secondary distilled water and absolute ethyl alcohol, drying to finally obtain Zn-BTC-MOF crystals, and further grinding into Zn-BTC-MOF powder;
step (2) a certain amount of cetyl trimethyl ammonium bromide is taken and dispersed in ethanol to obtain a mixed solution, and the mixed solution is stirred uniformly by ultrasound;
step (3), adding a proper amount of Zn-BTC-MOF into the mixed solution in the step (2), and performing ultrasonic treatment to form a uniform suspension;
step (4) a proper amount of tetraethyl orthosilicate is taken and released into ethanol, then the tetraethyl orthosilicate is dripped into the mixed solution in the step (3), the PH=9-11 of the solution is regulated by ammonia water, and the solution is stirred at room temperature; after the reaction is finished, centrifuging and washing for 2 to 5 times, and then drying in a drying oven at 50 to 80 ℃ to obtain the final product loaded with SiO 2 Zn-BTC-MOF material of (C).
2. The blow-moldable special super tough nylon of claim 1, wherein: in the step (1), trimesic acid and Zn (NO) 3 ) 2 The mass ratio of the NaOH solution is 1:1.5-2:2.5-3.2; the drying temperature in the step (1) is 50-80 ℃ and the drying time is 5-12 hours.
3. The blow-moldable special super tough nylon of claim 1, wherein: the mass ratio of Zn-BTC-MOF to cetyltrimethylammonium bromide is 1:0.1-0.5, and the mass ratio of Zn-BTC-MOF to tetraethyl orthosilicate is 1-10:1.
4. The blow-moldable special super tough nylon of claim 1, wherein: the PA6 is PA6 with standard viscosity of 2.5-2.7.
5. A method for preparing the blow-moldable special super-tough nylon as claimed in any one of claims 1 to 4, which is characterized in that: the preparation method comprises the following steps of calculating the mass fractions of the components: 70-90% of PA6 resin, 10-29% of compatilizer, 0.5-1% of Zn-BTC-MOF material loaded with SiO2 and 0.5-1% of other auxiliary agents, mixing the components, stirring for 10min by a stirrer, putting the mixture into a preheated double-screw machine for production at the main machine rotation speed of 400r/min, and putting the produced materials into a charging basket for drying and vacuum packaging.
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| WO2019175717A1 (en) * | 2018-03-14 | 2019-09-19 | Desiccant Rotors International Private Limited | Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof |
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